Amine Chemistry of Porous CO2 Adsorbents.

ConspectusAs renewable energy and CO2 utilization technologies progress to make a more significant contribution to global emissions reduction, carbon capture remains a critical component of the mission. Current CO2 capture technologies involve operations at point sources such as fossil fuel-based power plants or source-agnostic like in direct air capture. Each strategy has its own advantages and limitations, but in common, they all employ sorption-based methods with the use of sorbents strongly adhering to CO2. Amine solutions are the most widely used absorbents for industrial operations due to the robust chemical bonds formed between amines and CO2 under both dry and humid conditions, rendering excellent selectivity. Such strong binding, however, causes problematic regeneration. In contrast, purely physisorptive porous materials with high surface areas allow for the confinement of CO2 inside narrow pores/channels and have a lower regeneration energy demand but with decreased selectivity and capacity. The most promising solution would then be the unification of both types of sorbents in one system, which could bring about a practical adsorption-desorption process. In other words, the development of porous solid materials with tunable amine content is necessary to leverage the high contact surface of porous sorbents with the added ability to manipulate amine incorporation toward lower CO2 binding strength.To answer the call to uncover the most feasible amine chemistry in carbon capture, our group has devoted intense effort to the study of amine-based CO2 adsorbents for the past decade. Oriented along practicality, we put forth a principle for the design of our materials to be produced in no more than three synthetic steps with economically viable starting materials. Porous organic polymers with amine functionalities of various substitutions, meaning primary, secondary, and tertiary amines, were synthesized and studied for CO2 adsorption. Direct synthesis proved to be feasibly applicable for secondary and tertiary amine-incorporated porous polymers whereas primary-amine-based sorbents would be conveniently obtained via postsynthetic modifications. Sorbents based on tertiary amines exhibit purely physical adsorption behavior if the nitrogen atoms are placed adjacent to aromatic cores due to the conjugation effect that reduces the electron density of the amine. However, when such conjugation is inhibited, chemisorptive activity is observed. Secondary amine adsorbents, in turn, express a higher binding strength than tertiary amine counterparts, but both types can merit a strengthened binding by the physical impregnation of small-molecule amines. Sorbents with primary-amine tethers can be obtained via postsynthetic transformation of precursor functionalities, and for them, chemical adsorption is mainly at work. We conclude that mixed-amine systems could exhibit unprecedented binding mechanisms, resulting in exceptionally specific interactions that would be useful for the development of highly selective sorbents for CO2.

Hydrovoltaic Electricity Generator with Hygroscopic Materials: A Review and New Perspective.

The global energy crisis caused by the overconsumption of nonrenewable fuels has prompted researchers to develop alternative strategies for producing electrical energy. In this review, a fascinating strategy that simply utilizes water, an abundant natural substance throughout the globe and even in air as moisture, as a power source is introduced. The concept of the hydrovoltaic electricity generator (HEG) proposed herein involves generating an electrical potential gradient by exposing the two ends of the HEG device to dissimilar physicochemical environments, which leads to the production of an electrical current through the active material. HEGs, with a large variety of viable active materials, have much potential for expansion toward diverse applications including permanent and/or emergency power sources. In this review, representative HEGs that generate electricity by the mechanisms of diffusion, streaming, and capacitance as case studies for building a fundamental understanding of the electricity generation process are discussed. In particular, by comparing the use and absence of hygroscopic materials, HEG mechanism studies to establish active material design principles are meticulously elucidated. The review with future perspectives on electrode design using conducting nanomaterials, considerations for high performance device construction, and potential impacts of the HEG technology in improving the livelihoods are reviewed.

Highly Selective and Scalable Molecular Fluoride Sensor for Naked-Eye Detection.

Fluoride is widely present in nature, and human exposure to it is generally regarded as inevitable. High levels of fluoride intake induce acute and chronic illnesses. To reduce potential harm to the general public, it is essential to create selective fluoride detectors capable of providing a colorimetric response for naked-eye detection without the need for sophisticated equipment. Here, we report a one-pot synthesis of four different diaminomaleonitrile-derived Schiff base sensors. The terephthalaldehyde adduct provided a strong color change visible to the naked eye at a F- concentration level as low as 2 ppm. From the evaluation against other anions, such as CN-, I-, Br-, Cl-, NO3-, PO43-, OAc-, and HSO4-, the molecular sensor displayed a visible color change exclusively upon exposure to fluoride, underscoring exceptional selectivity. As a key intermediate for understanding the mechanism, HF2- was confirmed by 19F nuclear magnetic resonance. Theoretical calculations suggested a deprotonation-triggered bathochromic shift brought about by the unique electronic structure of the sensor. Furthermore, the simple synthetic protocol from economically accessible materials allowed for the preparation of the compound on a large scale, rendering it a highly practical visual fluoride sensor.

Photoenergy Harvesting by Photoacid Solution.

Solar energy has seen 180 years of development since the discovery of the photovoltaic effect, having achieved the most successful commercialization in the energy-harvesting fields. Despite its long history, even the most state-of-the-art photovoltaics remain confined to solid-state devices, limiting spatial and light utilization efficiencies. Herein, a liquid-state photoenergy harvester based on a photoacid (PA), a chemical that releases protons upon light irradiation and recombines with them in the dark through a fully reversible reaction, is demonstrated. Asymmetric light exposure on a PA solution contained in a transparent tube generates a pH gradient (ΔpH = 2) along the exposed and dark regions, which charges the Nernst potential up to 0.7 V across the two electrodes embedded at each end, as if a capacitor. Owing to the reversibility of PAs, a PA-driven liquid-state photoenergy harvester (PLPH) generates capacitive currents up to 0.72 mA m-2  on an irradiation. Notably, the transparent nature of the PLPH enables vertical stacking up to 25 units, which multiplies the light-harvesting efficiencies by over 1000%. This unique approach provides a new route to harness solar energy with a form-factor-free design that maximizes spatial and light-use efficiencies.

Multifunctional Filter Membranes Based on Self-Assembled Core-Shell Biodegradable Nanofibers for Persistent Electrostatic Filtration through the Triboelectric Effect.

The massive production of polymer-based respiratory masks during the COVID-19 pandemic has rekindled the issue of environmental pollution from nonrecyclable plastic waste. To mitigate this problem, conventional filters should be redesigned with improved filtration performance over the entire operational life while also being naturally degradable at the end. Herein, we developed a functional and biodegradable polymeric filter membrane consisting of a polybutylene adipate terephthalate (PBAT) matrix blended with cetyltrimethylammonium bromide (CTAB) and montmorillonite (MMT) clay, whose surface properties have been modified through cation exchange reactions for good miscibility with PBAT in an organic solvent. Particularly, the spontaneous evolution of a partial core-shell structure (i.e., PBAT core encased by CTAB-MMT shell) during the electrospinning process amplified the triboelectric effect as well as the antibacterial/antiviral activity that was not observed in naive PBAT. Unlike the conventional face mask filter that relies on the electrostatic adsorption mechanism, which deteriorates over time and/or due to external environmental factors, the PBAT@CTAB-MMT nanofiber membrane (NFM)-based filter continuously retains electrostatic charges on the surface due to the triboelectric effect of CTAB-MMT. As a result, the PBAT@CTAB-MMT NFM-based filter showed high filtration efficiencies (98.3%, PM0.3) even at a low differential pressure of 40 Pa or less over its lifetime. Altogether, we not only propose an effective and practical solution to improve the performance of filter membranes while minimizing their environmental footprint but also provide valuable insight into the synergetic functionalities of organic-inorganic hybrid materials for applications beyond filter membranes.

Lithium-Air Batteries: Air-Breathing Challenges and Perspective.

Lithium-oxygen (Li-O2) batteries have been intensively investigated in recent decades for their utilization in electric vehicles. The intrinsic challenges arising from O2 (electro)chemistry have been mitigated by developing various types of catalysts, porous electrode materials, and stable electrolyte solutions. At the next stage, we face the need to reform batteries by substituting pure O2 gas with air from Earth's atmosphere. Thus, the key emerging challenges of Li-air batteries, which are related to the selective filtration of O2 gas from air and the suppression of undesired reactions with other constituents in air, such as N2, water vapor (H2O), and carbon dioxide (CO2), should be properly addressed. In this review, we discuss all key aspects for developing Li-air batteries that are optimized for operating in ambient air and highlight the crucial considerations and perspectives for future air-breathing batteries.

CuFeO2-NiFe2O4 hybrid electrode for lithium-ion batteries with ultra-stable electrochemical performance.

Stable electrode materials with guaranteed long-term cyclability are indispensable for advanced lithium-ion batteries. Recently, delafossite CuFeO2 has received considerable attention, due to its relative structural integrity and cycling stability. Nevertheless, the low conductivity of delafossite and its relatively low theoretical capacity prevent its use as feasible electrodes for next-generation batteries that require higher reversible capacities. In this work, we suggest a simple and straightforward approach to prepare CuFeO2-NiFe2O4 by introducing Ni precursor into Cu and Fe precursor to form NiFe2O4, which exhibits higher capacity but suffers from capacity fading, through sol-gel process and subsequent heat treatments. The presence of both NiFe2O4 and CuFeO2 is apparent, and the heterostructure arising from the formation of NiFe2O4 within CuFeO2 renders some synergistic effects between the two active materials. As a result, the CuFeO2-NiFe2O4 hybrid sample exhibits excellent cycling stability and improved rate capability, and can deliver stable electrochemical performance for 800 cycles at a current density of 5.0 A g-1. This work is an early report on introducing a foreign element into the sol-gel process to fabricate heterostructures as electrodes for batteries, which open up various research opportunities in the near future.

Triangular Fixation Technique for Bicolumn Restoration in Treatment of Distal Humerus Intercondylar Fracture.

BACKGROUND: Distal humerus intercondylar fractures are intra-articular and comminuted fractures involving soft tissue injury. As distal humerus is triangle-shaped, parallel plating coupled with articular fixation would be suitable for bicolumn restoration in treatment of distal humerus intercondylar fracture. METHODS: This study included 38 patients (15 males and 23 females) who underwent olecranon osteotomy, open reduction and internal fixation with the triangle-shaped cannulated screw and parallel locking plates (triangular fixation technique). Functional results were assessed with the visual analog scale (VAS) scores, Mayo elbow performance (MEP) scores and Disabilities of the Arm, Shoulder and Hand (DASH) questionnaires. Anteroposterior and lateral elbow radiographs were assessed for reduction, alignment, fracture union, posttraumatic arthrosis, and heterotopic ossification, and computed tomography (CT) scans were used to obtain more accurate measurements of articular discrepancy. RESULTS: All fractures healed primarily with no loss of reduction. The mean VAS, MEP, and DASH scores of the affected elbow were not significantly different from those of the unaffected elbow (p = 0.140, p = 0.090, and p = 0.262, respectively). The mean degree of flexion was significantly lower in the affected elbow than in the unaffected elbow, but was still considered as functional (p = 0.001, > 100° in 33 of 38 patients). Two cases of articular step-offs (> 2 mm) were seen on follow-up CT scans, but not significantly higher in the affected elbow than in the unaffected elbow (p = 0.657). Binary logistic regression analysis revealed that only Association for Osteosynthesis (AO) type C3 fractures correlated with good/excellent functional outcome (p = 0.012). Complications occurred in 12 of the 38 patients, and the overall reoperation rate for complications was 10.5% (4 of 38 patients). CONCLUSIONS: Triangular fixation technique for bicolumn restoration was an effective and reliable method in treatment of distal humerus intercondylar fracture. This technique maintained articular congruency and restored both medial and lateral columns, resulting in good elbow function.

Factors Associated with Increased Healing Time in Complete Femoral Fractures After Long-Term Bisphosphonate Therapy.

BACKGROUND: The purpose of this study was to analyze factors that affect healing time after operative treatment of complete femoral fractures associated with long-term use of bisphosphonates. In particular, we sought to determine surgically controllable factors related to fracture-healing time. METHODS: Ninety-nine consecutive patients (109 fractures) who had been surgically treated for a complete atypical femoral fracture were enrolled. All patients had a documented history of bisphosphonate therapy at the time of presentation, with an average duration of 7.4 ± 3.5 years (range, 3 to 20 years). Baseline demographic data, characteristics of the fracture and surgery, and radiographic findings including femoral neck-shaft angle, coronal and sagittal bowing of the femur, and thickness of the femoral cortex were examined. Univariate and multivariate logistic regression analyses were performed to identify predictive factors associated with delayed union or nonunion. RESULTS: Of the 109 fractures, 76 (69.7%) showed osseous union within 6 months after the index surgery and were assigned to the successful healing group. The remaining 33 fractures (30.3%), which showed delayed union or nonunion, were assigned to the problematic healing group. There were differences in body mass index (BMI), bisphosphonate therapy duration, and the rate of prodromal symptoms between the 2 groups. Supra-isthmic fracture location, femoral bowing of ≥10° in the coronal plane, and a lateral/medial cortical thickness ratio of ≥1.4 were predictive of problematic healing but were uncontrollable factors. Iatrogenic cortical breakage around the fracture site as well as a ratio of ≥0.2 between the remaining gap and the cortical thickness on the anterior and lateral sides of the fracture site were controllable predictive factors associated with problematic healing. CONCLUSIONS: Intramedullary nailing without cortical breakage around the fracture site and decreasing the anterior and lateral fracture gaps (avoidance of distraction) as much as possible are recommended to reduce healing time in complete femoral fractures associated with long-term use of bisphosphonates. LEVEL OF EVIDENCE: Therapeutic Level IV. See Instructions for Authors for a complete description of levels of evidence.

Factors that Influence Reduction Loss in Proximal Humerus Fracture Surgery.

OBJECTIVES: This study was performed to identify the risk factors for reduction loss after locking plate fixation of proximal humerus fractures. DESIGN: Retrospective study. SETTING: University trauma center. PATIENTS AND INTERVENTION: We retrospectively evaluated 252 patients who had been surgically treated for proximal humeral fractures with locking plates between January 2004 and December 2011. MAIN OUTCOME MEASUREMENTS: Charts and standardized x-rays (true anteroposterior and axillary lateral views) were used to evaluate the Neer and AO OTA fracture types, initial neck-shaft angle (NSA, varus displacement), medial comminution, postoperative NSA (reduction adequacy), medial support restoration, healing progress, reduction loss, and implant-related problems immediately after surgery and at 2 weeks, 1 month, 3 months, 6 months, 9 months, and at least 1 year after surgery. Reduction loss was defined as (1) ≥10 of angulation in any direction, (2) ≥5 mm of height loss of the humeral head from the plate, and (3) fixation failure. RESULTS: Reduction loss occurred in 6.7% (17 of 252) of cases; revision surgeries were performed in all cases. Univariable logistic regression analysis revealed that older age (P = 0.023), osteoporosis (P = 0.001), varus displacement (P = 0.001), medial comminution (P = 0.001), reduction adequacy (P = 0.036), and insufficient medial support (P = 0.001) had significant correlations with reduction loss. CONCLUSIONS: Multivariable regression analysis revealed that osteoporosis (less than -2.5 bone mineral density, P = 0.015), displaced varus fracture (less than 110° of NSA, P = 0.025), medial comminution (more than 1 fragment, P = 0.018), and insufficient medial support (no cortical or screw support, P = 0.001) were independent risk factors for reduction loss in the proximal humerus fractures surgery. LEVEL OF EVIDENCE: Prognostic Level II. See Instructions for Authors for a complete description of levels of evidence.